Yellow methine dyes for hydrophobic textile material

ABSTRACT

Water insoluble disperse dyes for aromatic polyester textile material are made by the reaction of an aldehyde intermediate derived from an α-(N-alkylanilino)m-toluenesulfonamide, typified by α-(N-ethylanilino)-m-toluenesulfonamide, with a nitrile containing an active methylene group, such as malononitrile. This class of dyes, when appropriately dispersed, produces bright greenish-yellow dyeings on aromatic polyester fabrics with excellent substantivity, outstanding sublimation fastness, and excellent fastness to light. The dyes are applied to polyesters, such as polyethylene terephthalate, by carrier dyeing, pressure dyeing and thermofixation methods.

This is a division of application Ser. No. 248,483, filed Apr. 28, 1972,now U.S. Pat. No. 3,858,259.

BACKGROUND OF THE INVENTION

Among the polyester fibers, those based on polyethylene terephthalatecontinue to be the most important, although fibers based on1,4-dimethylcyclohexane terephthalate have become commerciallyavailable. Developments in both homo- and copolyesters have continuedand many modified versions of polyethylene terephthalate have recentlyappeared on the market. With the advent of new fibers, the search hascontinued for dyes which build up on the various types of polyesterfabric proportionate to the amount of dye applied, and which arecharacterized by good light and excellent sublimation properties.

In polyethylene terephthalate fibers, the diffusion of the dye into thefiber is effectively controlled by the mobility of the chain moleculesin the disordered regions. However, the molecular shape and the size ofthe dye, the presence of polar groups and general steric considerationsare also important in relation to the rate of diffusion.

Styryl dyes for aromatic polyester textile material are known from U.S.Pat. No. 3,635,957 of Guido R. Genta, the copending application of GuidoR. Genta, Ser. No. 227,296, filed Feb. 17, 1972, and U.S. Pat. No.3,349,098 of James M. Straley et al. We have discovered certain newwater insoluble styryl dyes provide exceptional results when applied tothe now available polyester fibers. These dyes can be applied by any ofthe standard methods and the resulting dyeings are characterized by goodlight fastness and outstanding sublimation properties.

SUMMARY OF THE INVENTION

In accordance with the invention, there is provided a dye of theformula: ##SPC1##

In the above formula, Y is cyano, benzyl, carbamoyl, N-lower alkylcarbamoyl, N,N-dilower alkyl carbamoyl, N-phenyl carbamoyl, N-loweralkoxy, phenylcarbamoyl, N-loweralkyl phenyl carbamoyl, N-halophenylcarbamoyl, lower carbalkoxy, lower carbcyanoalkoxy, phenyl sulfonyl,halophenyl sulfonyl, and lower alkylphenylsulfonyl; R₁ is lower alkyl,cyano lower alkyl or hydroxy lower alkyl and R₂, R₃ and R₄ are hydrogen,lower alkyl, lower alkoxy, chlorine or bromine. R₅ and R₆ are hydrogen,lower alkyl, cyano lower alkyl or hydroxy lower alkyl. Also R₅ and R₆when taken collectively form a 5 or 6 -membered ring which can includeone additional nitrogen or oxygen hetero atom. The term "lower" is usedin all cases to designate an alkyl or alkoxy group having up to 6 carbonatoms. The dyes are applied by carrier dyeing, pressure dyeing andthermofixation, using standard methods.

DETAILED DESCRIPTION

Preferred dyes of the invention are those of the formula: ##SPC2##

in which R₁ = CH₃, C₂ H₅ or CH₂ CH₂ CN; R₂ and R₃ = H or CH₃ ; R₄ = H;and R₅ and R₆ = H, CH₃, C₂ H₅ or CH₂ CH₂ CN. These and other dyes of theinvention are made by the procedures hereinafter described.

Aldehyde intermediates of the type required to make the dyes of theinvention are available by a method often referred as the"Vilsmeier-Haack" Reaction (Vilsmeier, A. and A. Haack, Bull. Soc. ChimFrance 1962 1989). The generalized statement of the reaction is:##SPC3##

in which a suitable N,N-disubstituted aniline is treated with a suitableformanilide or formamide in the presence of phosphorus oxychloride toyield a p-disubstituted aminobenzaldehyde.

Useful aldehyde intermediates are those of the formula: ##SPC4##

wherein R₁, R₂, R₃, R₄, R₅ and R₆ have the meanings given above.

To make the aldehyde intermediate, dimethyl formamide is placed in asuitable reactor and kept below 25°C, phosphorus oxychloride is addedslowly with stirring and the α-(N-alkylanilino)-m-toluenesulfonamide isadded thereto, preferably portionwise.

The reaction to form the aldehyde used in the subsequent condensationgenerally takes from 1-4 hours at a temperature of 80°-120°C, preferablyat 90°-95°C. After the reaction is complete the mass is allowed to coolto room temperature, generally over a period of 8-16 hours.

The intermediate is recovered in a conventional manner by drowning thereaction mass in ice water, neutralizing with alkali, separating theorganic phase and dissolving it in alcohol, crystallizing, filtering andwashing the crystals thus obtained with cold alcohol.

α-(N-alkylanilino)-m-toluenesulfonamides useful in preparing thealdehyde intermediates are made by chlorosulfonation of a suitabletertiary amine, followed by reaction with ammonia, a primary aliphaticamine or a secondary aliphatic amine. Tertiary amine bases which aresuitable for the chlorosulfonation reaction are made by the reactionbetween an N-alkylaniline and a benzyl halide. Particularly usefulcompounds resulting from this reaction includeα-(N-methylanilino)-m-toluenesulfonamide,α-(N-ethylanilino)-m-toluenesulfonamide,α-(N-cyanoethylanilino)-m-toluenesulfonamide,α-(N-methyl-m-toluidino)-m-toluenesulfonamide,α-(N-ethyl-o-chloroanilino)-m-toluenesulfonamide,α-(N-ethylanilino)-m-(6-chlorotoluenesulfonamide),α-(N-methylanilino)-m-(4-methoxytoluenesulfonamide),α-(N-ethylanilino)-m-(N,N-dimethyltoluenesulfonamide),α-(N-cyanoethylanilino)-m-(N-ethyltoluenesulfonamide),α-(N-methylanilino)-m-(N-cyanoethyltoluenesulfonamide), andα-(N-ethylanilino)-m-(N,N-dihydroxyethyltoluenesulfonamide).

The structure of these and other compounds are thus: ##SPC5##

The 4'-position is unsubstituted since it must be available as areaction site to be useful. The position of the sulfamyl group has beenassigned by analogy with the sulfonic acid studies of Blanguy, L, H.E.Fierz-David, G. Stamm, Helv. Chim. Acta. 25 1162 (1942) in which similarN-alkyl-N-arylbenzyl amines were sulfonated, yielding mainly thesubstituted m-toluenesulfonic acid, V=OH. However, other products wereisolated and must represent other positions of the entering sulfo group.Thus, it is highly presumptive that chlorosulfonation behaves similarly,and certain amounts of sulfonamides of the structure are formed. Theyare useful materials if the sulfonamide group is in the benzyl moiety.

It is possible to synthesize suitableN-alkylanilino-α-p-toluenesulfonamide by treating N-alkylanilinesunsubstituted in the para position with α-chloro (or bromo)-p-toluenesulfonamide and their N-substituted and N,N-disubstitutedderivatives. The method is not as attractive economically orprocedurally as in the chlorosulfonation method. Both series give dyesof the same excellent fastness ratings.

Useful nitriles are those of the formula: ##EQU1## in which Y is asdefined aforesaid. Particularly useful are malononitrile; ethylcyanoacetate; cyanoethyl cyanoacetate; methyl cyanoacetate;cyanoacetamide; N-methyl cyanoacetamide; cyanoacetanilide;cyanocet-o-anisidide; cyanoacet-p-toluidide;cyanoacet-(m-chloro)anilide; phenylsulfonylacetonitrile;p-tolylsulfonylacetonitrile; p-chlorosulfonylacetonitrile.

Along with the nitrile and the aldehyde intermediate, there is chargedto the reaction mixture an alcohol, such as ethanol or 2-propanol and asmall amount of piperidine to assist in the condensation reaction.

The condensation reaction is run at a temperature of 80°-120°C.,preferably 100°-105°C. After condensation is complete, which generallyrequires from about 11/2to 4 hours, the reaction mass is slowly cooledto below room temperature, preferably 10°-15°C. The product dyecrystallizes slowly from the reaction mixture at these temperature. Thedye is recovered by filtration and is subsequently washed with analcohol, such as 2-propanol, followed by cold water.

To prepare the product for application to the polyester substrates notedhereabove, it must be suitably dispersed. This may be done by any ofseveral well-known methods: milling as in a ball-mill with dispersingagents such as lignin sulfonic acid materials, for instance. Theresultant aqueous dispersion can be dried, as in a spray-dryer, orpreserved and used as a paste. Standardization to any desired lowerstrength can be done with inert colorless diluents such as inorganicsalts for powders, or water for pastes. Other materials such aspreservatives, foam-control agents, and wetting agents may be added asdesired.

Dispersed pastes are made by wet milling the dye in conventionalequipment in the presence of a dispersing agent, preferably sodiumlignin sulfonate or sodium alkylnaphthalene sulfonate. Various othercommercially available dispersing agents, such as sodium salts ofcarboxylated polyelectrolytes and the naphthalene sulfonates; e.g., thecondensation products of sulfonated naphthalene and formaldehyde, suchas sodium dinaphthylmethane disulfonate, are conveniently used. The oildisperse paste may be cut or standardized to a standard strength withwater. The final color content of the finished paste averages from 10-40percent by weight (pure color) active dye base.

Disperse powders are prepared by wet milling color in the presence of adispersant, such as those mentioned hereabove, in equipment such as aball mill, Werner-Pfleiderer mill or attritor. The dispersed material isoven or spray dried and micropulverized if necessary to provide thedispersed powder. The color is cut or standardized to a standardstrength in a blender with a diluent, such as sodium sulfate or dextrin.A wetting agent, such as sodium cetyl sulfate or an alkylphenoxypolyethanol may be added to aid in wetting out the product when it isplaced in the dye bath. Disperse powders are usually cut or standardizedto 25-60 percent by weight color content (pure color).

The dye, when added to water with or without auxiliary agents, forms anear colloidal aqueous dispersion from which the aromatic polyesterfiber or textile material is dyed in the conventional manner at40°-100°C (104°-212°F) to give a colored fiber containing about 0.01 -2percent by weight dye (100% color basis).

Alternatively, dyeing may be accomplished without a carrier attemperatures of 100°-150°C under pressure. Also, the dye may be appliedin patterns by conventional printing methods, if desired.

The dye can be also applied to the aromatic polyester fiber bythermofixation methods, such as the "Thermosol" process. This process,which involves padding the cloth with the diluted dye dispersionfollowed by drying and heating with dried hot air or heated contactrolls, is conveniently used for dyeing polyester fibers and blendscontaining these fibers. Fixation temperatures of 180°-220°C(356°-428°F) are used for 30 to 90 seconds. If the fabric containscotton or viscose rayon, apart from synthetic fibers, there is littledanger of damaging cellulosic portions, but if wool is present, thetemperature must be kept within 180°-200°C and the time must be reducedto 30 seconds.

In order to evaluate the effectiveness of a particular dye for a giventype of fiber, the dyed fiber is examined for substantivity of thecolor, light fastness of the color, and resistance of the color tosublimation. Specific tests for the evaluation of these importantproperties are described in the examples that follow.

The dyes of the invention may be used for the coloration of rigidplastic substrates. The rigid plastic substrates contemplated within thescope of the invention are those plastic materials capable of beingpigmented with the compounds of the invention, and will be referred toherein as "rigid plastic substrates". The rigid plastic substrates ofthe invention include those materials capable of being formed into ashaped article, including semi-rigid materials which may be deformed byapplication of pressure.

As rigid plastic substrates of the invention may be mentionedterpolymers, including acrylonitrile-styrene-butadiene, often known asABS; acrylics, including methacrylics; polystyrene, both foamed andrubber modified polysulfones; cellulosic derivatives, particularlyesters such as cellulose acetate, propionate and butyrate; polyamidessuch as nylon; epoxy and phenolic resins; polycarbonates; andpolyesters. It is understood that the rigid plastic substrates includethose materials capable of being pigmented with the compounds of theinvention, and therefore copolymers of the above classes of compounds,such as styrenebutadiene, are also within the scope of the invention.

Specific examples of thermoplastic resins include polyvinyl chloride,polyvinyl acetate, vinyl chloride/acetate copolymers, polyvinyl alcohol,polyvinyl acetal, ethylene/vinyl acetate, ethylene/vinyl propionate,ethylene/vinyl isobutyrate, ethylene/vinyl alcohol, ethylene/methylacrylate, ethylene/ethyl acrylate ethylene/ethyl methacrylate,ethylene/allyl alcohol, ethylene/allyl acetate, ethylene/allyl acetone,ethylene/allyl benzene, ethylene/allyl ether, ethylene/acrolein,polyhexamethylene adipamide, polyhexamethylene sebacamide,polycaprolactam, polymethyl methacrylate, polyacrylonitrile, polymethylacrylate, polyethyl methacrylate, and styrene/methyl methacrylate.

As preferred rigid plastic substrates of the invention may be mentionedthe polyacrylates, polystyrene and polycarbonates.

The rigid plastic substrates are colored with the compounds of theinvention through pigmentation processes. The compounds are admixed withthe plastic using sets of mixing rollers, mixing or milling apparatus.After the compounds and the plastic have been thoroughly mixed, theresultant colored mixture is shaped into the desired final form throughprocedures well known to those skilled in the art, such as pouring,calendering, extrusion, spreading, or injection molding. Where thedesired product is a semi-rigid material, plasticizers mayadvantageously be added prior to shaping into the desired final form. Asplasticizers suitable for this purpose may be mentioned esters ofphthalic acid. Although the plasticizer may be incorporated after themixing of the compound of the invention with the rigid plasticsubstrate, it also can be incorporated into the rigid plastic materialprior to mixing the pigment with the rigid plastic material. In order tovary the strength of the finished product or vary the color, it is alsopossible to add additional pigments or fillers in an amount sufficientto obtain the desired effect.

The amount of the compound of the invention which is used to color therigid plastic substrate may vary widely depending upon the degree ofcolor wished to be imparted to the final product, and depending uponwhether the compound of the invention is the sole colorant or whether itis used in admixture with other plastic colorants. When the compound ofthe invention is used in admixture with other colorants, obviously avery minute quantity may be used to produce a complementary effect.Generally, the amount of colorant comprises less than 15%, preferablyless than about 8%, by weight in relation to the rigid plasticsubstrate. An amount of colorant compound which has proved particularlyvaluable is about 0.0001% to about 1%.

Our invention is further illustrated by the following examples:

EXAMPLE 1 ##SPC6##

To a 500 ml. round bottom four-neck flask equipped with a stirrer, athermometer, a dropping funnel and a drying tube was charged 100 g.dimethylformamide. To this below 25°C was added dropwise while stirring58. g. phosphorus oxychloride. The was added in portions 118 g.N,N-dimethyl[α-(N-ethylanilino)]-m-toluenesulfonamide. The stirredcontents were slowly heated to 90°-95°C, held 2 hours at thattemperature, and then allowed to cool over 16 hours to room temperature.

To a beaker containing 2000 ml. water and ice was poured slowly thereaction mass above, the drowning bath never rising above 3°C.Neutralization of the drowned mass was carried out by slowly adding 25g. sodium hydroxide dissolved in 25 g. water, followed by 45 ml. sodiumacetate solution (20% by weight in water). The neutralization was donebelow 5°C, and Congo Red was used as an indicator. The supernatantliquid was decanted, and the residual viscous oil was dissolved in 250ml. hot denatured alcohol. Upon spontaneous cooling to room temperature,and further slow cooling to 10°C, yellow crystals separated, which wereseparated by filtration, washed sparingly with cold alcohol, and dried.

Weight, 105 g.; 80%. Mp. 80°-84°C (sinters, 78°c). Calc, N, 8.1%; found7.8%; Calc. S, 9.2%; found 7.8%.

EXAMPLE 1A ##SPC7##

To a one-liter round bottom four-neck flask equipped with a stirrer,thermometer, reflux condenser and heater was charged 69.2 g.N,N-dimethyl[α(N-ethyl-4-formylanilino)]-m-toluenesulfonamide, 150 g.dimethylformamide, 100 g. 2-propanol, 16.0 g. malononitrile and 5 g.piperidine. The mixture was heated slowly to 105°C, and stirred at theboil under reflux conditions for 2 hours. The heater was then turnedoff, and the mixture was stirred for 16 hours, during which time thetemperature came to that of the surroundings. The heater was removed andreplaced with a cooling bath, and the temperature was lowered to 5°Cover several hours and the contents allowed to stir for 2 hours at 5°C.The yellow crystals present were separated on a filter and washed withfirst 120 ml. 2-propanol, then ca 200 ml. cold water. The product wasdried at 80°C. MP. 147°-148°C. Calc, N, 14.2%; found 14.4%. Calc, S,8.1; found 7.9%.

To a ball-mill was charged 27.0 g. yellow methine product, 27.0 g."Lignosol FTA", (a commercially available ligninsulfonic acid dispersingagent) and 126.0 g. water. Milling was carried on until a satisfactorydispersion had been achieved as shown by filter tests.

The dyes of the invention can also be applied from organic solventsolution, for example solutions of perchloroethylene containing 20 to60% water and, if desired, up to 5% dimethyl sulfoxide.

EXAMPLE 1B

Application of the disperse dye to polyester terephthalate by theestablished dyeing methods of carrier, pressure and thermofixationyielded brilliant yellow dyeings of outstanding fastness to sublimation,light exposure, and washing as described hereafter. Strength, build-upand staining behavior on hydrophilic fibers was also excellent.

An aqueous dye bath containing 10% Marcron L (a commercially availablephenolic dye carrier) and 1% monosodium phosphate as a buffering agentwas prepared. Type 54 "Dacron" polyester fabric was treated in a bath at120°C for 10 minutes, the fabric-to-water dye bath ratio being 1:40. Thedisperse dye made as described in Example 1A was added in an amountsufficient to provide a bath containing 0.4% dye based on the weight ofpolyester fibers. Dyeing was continued for 1 hour at 205°F and thefabric was removed from the bath, rinsed and dried. Sample dyeings weretested for sublimation according to standard AATCC Color Fastness to DryHeat (sublimation) Test No. 117-1967T, Page 123 of the 1970 TechnicalManual of the American Association of Textile Chemists and Colorists.Dyed fabric was placed between a sandwich of undyed "Dacron" polyesterfabric and heat was applied for 30 seconds. Sublimation tests were madeat 350°F and 400°F on goods as described above. The dyeing wascharacterized by bright greenish-yellow hue. Sublimation tests shownedsubstantially no transfer of color, even at 400°F.

Similar excellent results were obtained when the dye was applied to thefabric by pressure and thermofixation methods and then tested forsublimation as described above.

The dyeings were also tested for light fastness by subjecting them tocarbon arc fading in accordance with AATCC. Color Fastness to Light,Carbon Arc Lamp, Continuous Light Test No. 16A-1964, as detailed on p.127, of the 1970 Technical Manual of the AATCC. The dyeings showedsubstantially no break at 20 hours' exposure, indicating excellentfastness to light.

EXAMPLE 2 ##SPC8##

By treating an equivalent amount ofα-(N-ethylanilino)-m-toluenesulfonamide as described in Example I,α-(N-ethyl-4-formylanilino)-m-toluenesulfonamide could be prepared insimilar yield.

EXAMPLE 2 A ##SPC9##

In the manner described in Example 1A, an equivalent amount ofα-(N-ethyl-4-formylanilino)-m-toluenesulfonamide could be treated withmalononitrile to yield a methine dye of the structure given. Afterdispersion the structure could be applied to polyester terephthalatefabric by recognized dyeing methods as mentioned in Example 1A.Brilliant greenish-yellow hues were obtained which had the same gooddurability to degradative agents as did the dyeings of Example 1A.

EXAMPLE 3 ##SPC10##

The benzaldehyde whose synthesis is described in Example I was treatedwith an amount of ethyl cyanoacetate equivalent to the malononitrile andunder the same conditions as described in Example 1A. A methine dye ofthe above structure was obtained. After dispersion it was applied topolyester terephthalate fabric by established methods to yield brightgreenish-yellow dyeings of excellent fastness properties. Thesublimation fastness was particularly outstanding.

EXAMPLE 4 ##SPC11##

The benzaldehyde whose synthesis is described in Example 2A was treatedwith cyanoacet-o-toluidide in an amount equivalent to that given formalononitrile in Example 2A, and under the same conditions. A methinedye of the indicated structure was achieved. After dispersion andapplication to polyester fabric, it yielded brilliant greenish-yellowdyeings of properties comparable to the ones mentioned in Example 1A.The strength of the dye in equal weights was less; the sublimationfastness was somewhat superior.

EXAMPLE 5 ##SPC12##

The benzaldehyde of Example I was treated with an amount of cyanomethylphenyl sulfone equivalent to the malononitrile of Example 1A, and underthe same conditions. A methine body of structure as indicated wasachieved. After dispersion, it was applied to polyester fabrics to yieldbrilliant greenish-yellow dyeings of excellent fastness properties,particularly to sublimation.

EXAMPLES 6 - 49

By following the procedures given in the previous examples the followingbright greenish-yellow dyes are prepared. The dyes thus prepared whenapplied to aromatic textile material give excellent light and fastnessproperties.

                                      TABLE I                                     __________________________________________________________________________    EXAMPLES 6 to 49                                                              EX R.sub.1                                                                             R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                            R.sub.5 R.sub.6                                                                            Y                                        __________________________________________________________________________    6  CH.sub.3                                                                            H    3-CH.sub.3                                                                         H    CH.sub.3                                                                              H                                             7  n-C.sub.4 H.sub.9                                                                   H    H    H    CH.sub.2 CH.sub.2 OH                                                                  CH.sub.2 CH.sub.2 OH                                                               CONH.sub.2                               8  C.sub.2 H.sub.5                                                                     H    3-CH.sub.3                                                                         H    C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                    CN                                       9  C.sub.2 H.sub.5                                                                     2-Br H    H    H       H    CN                                       10 C.sub.2 H.sub.5                                                                     H    H    4-CH.sub.3                                                                         CH.sub.3                                                                              CH.sub.3                                                                           CN                                       11 C.sub.2 H.sub.5                                                                     2-CH.sub.3                                                                         5-Cl H    H       H    CN                                       12 CH.sub.3                                                                            2-Cl H    H    H       H    CONHCH.sub.3                             13 n-C.sub.3 H.sub.7                                                                   2-OCH.sub.3                                                                        5-CH.sub.3                                                                         H    CH.sub.3                                                                              H    CN                                       14 CH.sub.2 CH.sub.2 OH                                                                H    H    H    CH.sub.2 CH.sub.2 CN                                                                  H    CN                                       15 C.sub.2 H.sub.5                                                                     H    H    4-Cl H       H    CONHC.sub.2 H.sub.5                      16 CH.sub.3                                                                            H    H    H    CH.sub.2 CH.sub.2 OH                                                                  H                                             17 C.sub.2 H.sub.5                                                                     H    H    H    CH.sub.2 CH.sub.2 OCH.sub.3                                                           H    CN                                       18 CH.sub.3                                                                            2-OCH.sub.3                                                                        5-OCH.sub.3                                                                        H    CH.sub.3                                                                              CH.sub.3                                      19 C.sub.2 H.sub.5                                                                     H    H    4-Br C.sub.2 H.sub.5                                                                       H    CN                                       20 C.sub.2 H.sub.5                                                                     H    3-Br H    CH.sub.3                                                                              CH.sub.3                                      21 CH.sub.2 CH.sub.2 CN                                                                H    H    H    CH.sub.3                                                                              CH.sub.3                                      22 C.sub.2 H.sub.5                                                                     2-OCH.sub.3                                                                        H    H    H       H    CN                                       23 C.sub.2 H.sub.5                                                                     2-Cl                                                                 5Cl                                                                              H     CH.sub.3                                                                           H    COOCH.sub.3                                                24 C.sub.2 H.sub.5                                                                     H    H    4-OCH.sub.3                                                                        C.sub.2 H.sub.5                                                                       CH.sub.3                                                                           COOCH.sub.3                              25 CH.sub.3                                                                            H    H    H    CH.sub.3                                                                              CH.sub.3                                                                           CN                                       26 CH.sub.2 CH.sub.2 CN                                                                H    H    H    H       H    CN                                       27 C.sub.2 H.sub.5                                                                     H    H    H    CH.sub.2 CH.sub.2 CN                                                                  CH.sub.2 CH.sub.2 CN                          28 C.sub.2 H.sub.5                                                                     H    H    H    CH.sub.3                                                                              H                                             29 C.sub.2 H.sub.5                                                                     H    H    H    R.sub.5 and R.sub.5 taken                                                                  CN                                                               together                                              30 C.sub.2 H.sub.5                                                                     2-Br H    H    CH.sub.3                                                                              CH.sub.3                                                                           CON(CH.sub.3).sub.2                      31 C.sub.2 H.sub.5                                                                     H    H    H    CH.sub.3                                                                              CH.sub.3                                                                           COOCH.sub.2 CH.sub.2 OH                  32 C.sub.2 H.sub.5                                                                     2-CH.sub.3                                                                         5-Cl H    H       H    CON(CH.sub.2 CH.sub.2 CN).sub.2          33 C.sub.2 H.sub.5                                                                     H    H    H    C.sub.4 H.sub.9                                                                       H    SO.sub.2 CH.sub.3                        34 CH.sub.2 CH.sub.2 OH                                                                2-Cl H    H    CH.sub.3                                                                              CH.sub.3                                                                           CONHCH.sub.2 CH.sub.2 CN                 35 CH.sub.3                                                                            H    H    H    CH.sub.2 CH.sub.2 CN                                                                  CH.sub.2 CH.sub.2 CN                                                               SO.sub.2 C.sub.2 H.sub.5                 36 C.sub.2 H.sub.5                                                                     2-OCH.sub.3                                                                        5-CH.sub.3                                                                         H    CH.sub.3                                                                              CH.sub.3                                                                           COOCH.sub.2 CH.sub.2 Cl                  37 C.sub.2 H.sub.5                                                                     2-OCH.sub.3                                                                        5-CH.sub.3                                                                         H    C.sub.2 H.sub.5                                                                       H    CON(CH.sub.2 CH.sub.2 OH).sub.2          38 C.sub.2 H.sub.5                                                                     2-OCH.sub.3                                                                        5-CH.sub.3                                                                         H    H       H    COOCH.sub.2 CH.sub.2 OCH.sub.3           39 CH.sub.2 CH.sub.2 CN                                                                H    H    H    CH.sub.3                                                                              CH.sub.3                                                                           CONHCH.sub.2 CH.sub.2 OH                 40 C.sub.2 H.sub.5                                                                     H    H    H    CH.sub.2 CH.sub.2 OH                                                                  CH.sub.2 CH.sub.2 OH                          41 C.sub.2 H.sub.5                                                                     H    H    H    CH.sub.3                                                                              CH.sub.3                                      42 CH.sub.3                                                                            2-Cl H    H    H       H    COOCH.sub.2 CH.sub.2 OC.sub.2                                                 H.sub.5                                  43 CH.sub.3                                                                            H    H    H            H    CONHCH.sub.2 CH.sub.2 Cl                 44 CH.sub.2 CH.sub.2 CN                                                                H    H    H    CH.sub.3                                                                              CH.sub.3                                                                           COOCH.sub.2 CH.sub.2 Br                  45 CH.sub.2 CH.sub.2 CN                                                                H    H    H    CH.sub.2 CH.sub.2 CN                                                                  H    COOCH(CH.sub.3).sub.2                    46 C.sub.2 H.sub.5                                                                     2-OCH.sub.3                                                                        5-CH.sub.3                                                                         H    H       H                                             47 C.sub.2 H.sub.5                                                                     2-OCH.sub.3                                                                        5-CH.sub.3                                                                         H    CH.sub.2 CH.sub.2 CN                                                                  H                                             48 CH.sub.3                                                                            H    H    H    CH.sub.2 CH.sub.2 CN                                                                  H                                             49 C.sub.2 H.sub.5                                                                     H    H    H    H       H                                             __________________________________________________________________________

EXAMPLE 50 ##SPC13##

In the manner described in Example 1, an equivalent amount ofα-(N-ethyl-m-toluidino)-m-toluenesulfonamide was converted toα[N-ethyl(4-formyl-3-toluidino)]m-toluenesulfonamide. This was treatedwith malononitrile in the manner described in Example 1A to yield amethine dye of the structure given. Brilliant yellow shades of excellentstrength were obtained on polyethylene terephthalate.

EXAMPLE 51 ##SPC14##

In the manner of Example 50,α[N-3-cyanoethyl(4-formyl-3-toluidino)]m-toluenesulfonamide was treatedwith malononitrile. Dyeings of the dispersed dye on polyesterterephthalate were brilliant yellows of excellent strength,lightfastness and sublimation.

EXAMPLE 52

Methylmethacrylate resin is colored with the compound of Example 1A asthe colorant, in a ratio of 2 grams resin to 1 mg. colorant. The resinis prepared by placing 1 pound of methylmethacrylate into a Thropp mill(a 2-roller mill), which is then heated and run in order to melt andsmash the resin to a molten mass. The compound of Example 1A is addedand the entire mixture of resin and colorant is milled until thecolorant is uniformly distributed in the mass as measured by eye. Whilestill hot, 30 grams of the hot mass is cut off for use in the followingprocedure. The sample, containing 30 grams methylmethacrylate and 15 mg.of the compound of Example IA as colorant, may be conveniently molded ina Laboratory 40 Single Acting Watson-Stillman Laboratory Press(Farrell-Birmingham Co. 50-ton press). 30 grams of methylmethacrylatemixture containing 15 mg. of the compound of Example 1A per pound ofmethylmethacrylate is placed in the cold mold, which is then closed withthe Schrader Valve. The drain is opened and steam is applied to themold. When steam comes through the drain pipe, the drain is closed. Upto 25.0 tons pressure is exerted on the chips until the mold is fullyclosed. This can conveniently be accomplished by observing the pressuregauge. When the gauge needle no longer decreases in pressure, the moldis then closed.

The mold is held closed at zero pressure by releasing the hydraulicpressure and maintaining the steam for 5 minutes. The mold pressure isincreased to 10 tons and held for 10 minutes, the steam remaining on.

The mold pressure is increased to 15 tons and the steam shut off; thedrain is opened and cooling water is added for 5 minutes. Thereafter thepressure is changed to zero and the mold is opened to extract theresultant plastic chip.

EXAMPLE 53

When the 30 grams of methylmethacrylate are replaced by 2 poundspolystyrene and 10.44 grams titanium dioxide, the procedure of Example52 being otherwise followed, a fast coloration of the polystyrene isobtained.

EXAMPLE 54

The compounds of the invention may also be used as colorants forplastics made from polycarbonates. A pigmented plastic material ofpolycarbonates and the compound of Example 1A may be prepared accordingto the following procedure:

A specimen is prepared by dry mixing pelletized or powdered resin withfinely divided colorant until uniform distribution is achieved of thecolorant in the resin material. Plasticizer may also be added, ifdesired. The mixture is then extruded or injected molded under suitableconditions. 454 gms. Lexan 121-R (General Electric) pellets are placedin Bipel 1 ounce reciprocating screw injection molder. The pellets aretumbled for 5 minutes on the barrel tumbler. The resin is heated (frontzone temperature of 550°F and rear zone temperature of 500°F) and chipsare produced from the virgin resin until chips of good quality areobtained. When the desired quality of chips are obtained with the clearresin, a fresh batch of Lexan 121-R, containing the compound of Example1A in an equivalent amount corresponding to Example 52 to produce apigmented plastic material is fed into the injection molder, to producepigmented chips having excellent fastness characteristics.

EXAMPLE 55

When the compounds of Examples 2A-49 are substituted for the compound ofExample 1A in the process of Example 52, methylmethacrylate is coloredto produce a greenish-yellow shaped plastic material. The compounds ofExamples 2A-49 may be used to impart coloration to polystyrene followingthe procedure of Example 53, and polycarbonate is pigmented with thecompounds of Examples 2A-49 following the procedure of Example 54.

We claim:
 1. A dye of the formula: ##SPC15##wherein Y is a memberselected from the group consisting of cyano, benzyl, carbamoyl, N-loweralkyl carbamoyl, N,N-dilower alkyl carbamoyl, N-phenylcarbamoyl,N-loweralkoxy phenylcarbamoyl, N-loweralkyl phenyl carbamoyl,N-halophenyl carbamoyl, lower carbalkoxy, lower cyanocarbalkoxy, phenylsulfonyl, halophenyl sulfonyl, and lower alkylphenylsulfonyl; R₁ is amember selected from the group consisting of lower alkyl, hydroxy loweralkyl and cyano lower alkyl; R₂, R₃ and R₄ are members selected from thegroup consisting of hydrogen, lower alkyl, lower alkoxy, chlorine andbromine, and R₅ and R₆ are members selected from the group consisting ofhydrogen, lower alkyl, cyano lower alkyl and hydroxy lower alkyl andtaken collectively form a 5 or 6-membered ring structure containing anadditional nitrogen or oxygen hetero atom.
 2. The dye of claim 1 whereinY is cyano, R₂, R₃, R₄, R₅ and R₆ are hydrogen; and R₁ is ethyl.
 3. Thedye of claim 1 wherein Y is cyano, R₂, R₃ and R₄ are hydrogen; R₅ and R₆are methyl; and R₁ is ethyl.
 4. The dye of claim 1 wherein Y isN-tolylcarbamoyl; R₂, R₃, R₄, R₅ and R₆ are hydrogen; and R₁ is ethyl.5. The dye of claim 1 wherein Y is carbethoxy; R₂, R₃ and R₄ arehydrogen; R₅ and R₆ are methyl; and R₁ is ethyl.
 6. The dye of claim 1wherein Y is phenylsulfonyl, R₂, R₃ and R₄ are hydrogen; R₅ and R₆ aremethyl; and R₁ is ethyl.
 7. A dye of the formula: ##SPC16##in which R₁is methyl, ethyl or cyanoethyl; R₂ and R₃ are hydrogen or methyl: R₄ ishydrogen and R₅ and R₆ are hydrogen, methyl, ethyl or cyanoethyl.
 8. Thedye of claim 7 in which R₁ is ethyl, R₃ is methyl and R₂, R₄, R₅, and R₆are hydrogen.
 9. The dye of claim 7 in which R₁ is cyanoethyl, R₃ ismethyl and R₂, R₄, R₅ and R₆ are hydrogen.